Catalyst systems for two-pack acrylic adhesive formulations

ABSTRACT

Disclosed are novel catalyst systems and method for curing a peroxide-curable ethylenically unsaturated (e.g. acrylic or vinyl) composition wherein the catalyst system is a combination of the peroxide curing agent and a Cu +1  activator or a combination of a peroxide curing agent and an activator system comprising a furfuryl alcohol and an acid catalyst. Also disclosed is a new catalyst system for curing ring compounds (e.g. epoxides) which comprises a combination of ferrocene and a diazonium salt of a Lewis acid. Preferred curable compositions are adhesives and especially acrylic adhesives and epoxy adhesives.

BACKGROUND OF THE INVENTION

The present invention relates to two-pack acrylic adhesive formulationsand more particularly to novel catalyst systems therefor.

The use of structural adhesives has increased substantially in recentyears in the aircraft, housing and construction, automotive and footwearindustries, to name but a few large quantity users of such adhesives.The trend to structural adhesive formulations has been facilitated bythe replacement of conventional metal and ceramic materials by polymersand by the development of a new generation of adhesives which are toughand can be applied quickly without burdensome surface preparation.Unlike conventional epoxy adhesive formulations which generally cureslowly and required careful mixing and surface preparation techniques,the second generation acrylic adhesives contain catalysts and promoterswhich promote rapid, room temperature cure and obviate the need formeticulous surface preparation and proportional mixing of components.Moreover, such second generation acrylic adhesive formulations possessexcellent strength which is derived through special tougheningmechanisms.

A variety of catalyst systems have been developed for reactive acrylicadhesive formulations. For example, prior catalyst systems include thecombination of a tertiary amine and a peroxide (U.S. Pat. No.3,333,025); aldehyde/amine condensation products in combination withcertain chelates (U.S. Pat. No. 3,591,438); amines plus benzoyl peroxide(U.S. Pat. Nos. 3,725,504 and 3,832,274); a redox system of cobaltnapthanate and MEK hydroperoxide (U.S. Pat. No. 3,838,093); thecombination of amines, salts of transition metals, amine-aldehydecondensation products, and peroxides (U.S. Pat. No. 3,890,407); aminesand peroxides in combination with oxidizable metal ions (U.S. Pat. No.3,994,764); saccharin or copper saccharate and para-toluene sulfonicacid (U.S. Pat. No. 4,052,244); and peroxides and amine-aldehydecondensation products with a non-transition metal including lead, zinc,tin, calcium, strontium, barrium, and cadmium (U.S. Pat. No. 4,230,834).U.S. Pat. No. 3,855,040 shows a combination of a peroxy initiator, astrong acid, and ferrocene. Relative to the use of transition metals ortransition metal salts as accelerators, U.S. Pat. No. 4,230,834 showsthat the use of any transition metal ion accelerator, especially copper,causes poor bonding or low tensile strength values when compared to thenon-transition metal ion accelerators disclosed therein.

BROAD STATEMENT OF THE INVENTION

Broadly, the present invention is a method for curing a peroxide-curableethylenically unsaturated (eg. acrylic) composition of the type havingat least one ethylenic-functional compound selected from anethylenic-functional monomer, oligomer, polymer, or mixtures thereof,and a peroxide curing agent. The improvement in such method foractivating the peroxide curing agent comprises blending an activatorwith said acrylic composition to activate said peroxide to rapidly curethe ethylenic-functional compound. The activator is selected from thegroup consisting of:

(a) Cu⁺¹ ; and

(b) furfuryl alcohol and an acid catalyst.

The curable composition or mixture desirably is a structural acrylicadhesive containing specialized, toughened acrylic compounds and issupplied in two packages. The activators are combined with the peroxidejust prior to application as rapid initial set up of the acryliccomposition follows such blending.

The Cu⁺¹ activator can be dispersed in one of the adhesive packages neator can be complexed with any compound containing a hydroxyl group or anon-aromatic unsaturated group. The substrate bearing the Cu⁺¹ can beone of the reactive (eg. acrylic) components in the curable composition,a thermoplastic additive, or any other component contained therein. Avariety of novel complexes in acrylic adhesive technology resultsthereby.

The reaction of a furfuryl alcohol or furfuryl alcohol resin with acationic or acid catalyst results in the generation of heat adequate toresult in the generation of free radicals from a peroxide initiator forthe curing of ethylenic, eg. acrylic and vinyl, reactive components.Note also that a furan resin would result also.

A novel adhesion promoter for acrylic adhesive formulations comprises:##STR1## where

D is an organic group containing curable ethylenic unsaturation;##STR2##

B is an organic group containing no curable ethylenic unsaturation (eg.an epoxide group).

The novel adhesion promoter can be complexed with the Cu⁺¹ activator andprovides improved adhesion, boiling water resistance, and solventresistance.

A further invention is a catalyst system for effecting ring-opening cure(eg. epoxides) wherein the catalyst system comprises ferrocene and anaryl diazonium salt of a Lewis acid. This novel catalyst system alsowill effect the furfuryl alcohol cure described above.

Advantages of the present invention include the development of novelcatalyst systems and methods for rapidly curing peroxide-curableformulations such as acrylic adhesive formulations without applicationof heat. Another advantage is that the catalyst systems do not detractfrom bond strength or other adhesive properties, but can enhance theperformance and properties of the cured acrylic composition. Anotheradvantage is the impressment of additional curing mechanisms into thesystem for providing truly unique, specialty acrylic adhesiveformulations. These and other advantages will be readily apparent tothose skilled in the art based upon the disclosure contained herein.

DETAILED DESCRIPTION OF THE INVENTION

In its broadest aspects, the present invention provides novel activatorswhich activate a peroxide catalyst or initiator for achieving the cureof an acrylic, vinyl, or like ethylenically unsaturated compositioncapable of being cured by a peroxide initiator. For ease of descriptiononly, the peroxide-curable ethylenically unsaturated component oftenwill be described as an acrylic (or vinyl) compound as acrylic adhesivesare a preferred embodiment of the present invention. No limitation onthe invention should be inferred. Referring now to the use of a Cu⁺¹activator, the Cu⁺¹ activator functions as a reducing agent foractivating a peroxide initiator because the Cu⁺¹ activator loses anelectron according to the following reaction mechanism:

    Cu.sup.+1 →Cu.sup.+2 +1e.sup.-

    RO-OR (peroxide)+1e.sup.- →RO.sup.- +RO. (oxidizing agent)

The foregoing reaction system should be contrasted to the prior use ofCu⁺² (U.S. Pat. No. 4,052,244) in which the Cu⁺² gains an electronmaking the Cu⁺² an oxidizing catalyst. In this regard see the followingtext, Hogness and Johnson, "Qualitative Analysis and ChemicalEquilibrium", Henry Holt & Company, New York, N.Y., p. 89 (1954), thedisclosure of which is expressly incorporated herein by reference.Several important observations can be made relative to the functioningof the Cu⁺¹ activator as a reducing agent for activating a peroxideinitiator. Initially, the loss of an electron by Cu⁺¹ occurs at roomtemperature as does the reaction of the generated electron with theperoxide initiator. The spontaneous room temperature reaction sequence,then, concludes with the peroxide initiator initiating the free radicalcure of the acrylic or vinyl resin in the composition. This roomtemperature reaction is very rapid with set times for acrylic adhesivesas short as about 1-4 minutes being common. Since this spontaneousreaction is rapid at room temperature, the Cu⁺¹ activator and peroxideinitiator necessarily must be separated prior to cure. A two-packformulation is appropriate. Another very important observation is that,contrary to U.S. Pat. No. 4,230,834 which shows that a Cu⁺² catalyst isdetrimental to adhesive performance, the examples of the presentinvention clearly show that the Cu⁺¹ activator positively contributes toimproved performance of an acrylic adhesive formulation. Accordingly,the Cu⁺¹ activator serves a unique dual function in providing roomtemperature cure while improving performance of the resulting curedcomposition.

While the Cu⁺¹ activator can function effectively at room temperature,it can be quite advantageous on occasion to combine the Cu⁺¹ activatorwith a reducing agent for making a highly effective redox activatorcomposition. Note that the use of Cu⁺² in combination with a reducingagent for generation of a Cu⁺¹ activator is encompassed within theprecepts of the present invention. The preferred reducing agent isascorbic acid due to its rapid and effective interaction for ensuring aCu⁺¹ activator and its relative innocuousness with the remainder of thecurable composition and with substrates (eg. metals) to which thecomposition is applied. The presence of the reducing agent furtherensures the Cu⁺¹ form of copper being present. Other suitable reducingagents for generation Cu⁺¹ (cuprous) ions from Cu⁺² (cupric) ions,include, for example, sodium sulfite, sodium bisulfite, sodiummetabisulfate, and the like reducing agents. Further information on thiscan be found in Organic Synthesis, Collective Vol. 1, p. 170 or Vol. 2,p. 131, John Wiley & Sons, New York, N.Y. (1961), the disclosure ofwhich is expressly incorporated herein by reference.

The Cu⁺¹ activator can be supplied neat as a powder, as a halide salt,or an organic soluble compound such as copper (I) triflate, CuOSO₂ CF₃,[J. Am. Chem. Soc. 95, 1889 (1973)]. Another method for incorporatingthe Cu⁺¹ activator into a composition is to form a Cu⁺¹ olefin complexor a Cu⁺¹ hydroxyl complex. Further information on these complexes canbe found in the following references: Cotton and Wilkinson, "AdvancedInorganic Chemistry", 3d Ed. Chapter 23, John Wiley & Sons, New York,N.Y. (1972); "Inorganic and Organometallic Photochemistry", M. S.Wrighton, Editor, ACS-Advances in Chemistry Series 168 (1978); andSrinivasan, J. Am. Chem. Soc., 85, 3048 (1963), the disclosures of whichare expressly incorporated herein by reference. The substrates orcarriers with which the Cu⁺¹ complexes can be a monomer, oligomer, orpolymer including acrylic and vinyl reactive compounds, thermoplasticadditives, plasticizers, or any other conponent included within thecomposition. Many novel Cu⁺¹ complexes, thus, can be made, especially inthe reactive adhesive area. For reactive acrylic adhesive formulations,the following components are ideally adapted for use in adhesiveformulations and form complexes with the Cu⁺¹ accelerator: ##STR3##where R₁ is --H, ##STR4## where R₂ is ##STR5## R₃ is --H or --CH₃,##STR6## where R₄ is H or a lower alkyl group,

X is --O--, ##STR7## where Z is --CH₂ --CH₂ --O--_(n).

The foregoing list is exemplary as a variety of conventional hydroxy andnonaromatically unsaturated compounds will form suitable complexes withthe Cu⁺¹ activator according to the precepts of the present invention.Advantages for utilizing the Cu⁺¹ complexes for providing the Cu⁺¹activators include the improvement in properties (eg. tensile strength)which the activator provides, the improved availability of the activatorfrom the complex, and like advantages. The proportion of Cu⁺¹ activatorused in the curable composition is a catalytic proportion adequate toactivate the peroxide initiator for achieving cure and generally suchproportion is between about 0.1% and 5% by weight of the curablecomposition.

During the course of research on complexing of Cu⁺¹ with variousunsaturated resins, a new curable resin was discovered which possessesimproved adhesion, solvent resistance, and boiling water resistance.This new resin has the following structure: ##STR8## Where,

R₅ and R₆ are --H or --CH₃,

n is an integer of 1-6, ##STR9##

B is an organic group containing no curable unsaturation. Preferably, Bis

    --O--R.sub.7,

where,

R₇ is an epoxy group, a urethane group, or any organic group containingno curable unsaturation.

The new sulfide/sulfone resins can be complexed with the Cu⁺¹ activator,if desired.

Such resins can be synthesized from the following starting materials:##STR10## by their reaction with epichlorhydrin or the like, accordingto the reaction procedure found in Sorenson and Campbell, PreparativeMethods of Polymer Chemistry, pages 464-465, Interscience Publishers,New York, N.Y. (1968), the disclosure of which is expressly incorporatedherein by reference. The resulting molecules then are reacted with anacrylic acid or similar compound containing curable unsaturation forforming an unsymmetrical reactive resin. The residual epoxide group canbe left, or reacted further with isocyanate, an alcohol, glycol,alkylene oxide, carboxylic acid, or the like, wherein no curableunsaturation is contained in such reactant. The unreactive tail or chainis important for achieving improved adhesion, solvent resistance, andboiling water resistance compared to an equivalent resin containing tworeactive groups, eg. Japanese Pat. No. 56-34204.

The second method for activating the peroxide cure of peroxy-curableethylenically unsaturated compound utilizes a dual-cure scheme wherein afurfuryl alcohol resin is formed in the presence of a strong acidcatalyst. The heat generated in the furan polymer formation issufficient for activating the peroxide initiator and, thereby, curingthe curable ethylenically unsaturated compound. The resulting curednetwork consists of a combination of acrylic or vinyl, for example,polymer and a cured furfuryl alcohol polymer. The proportion of furfurylalcohol resin formed can be adjusted for providing specific performancerequirements unique to this embodiment of the present invention. Theincreased chemical resistance imparted by the furfuryl alcohol resin canbe important on occasion. General properties of furfuryl alcohol resinsand furfuryl alcohol-formaldehyde resins can be found in Encyclopedia ofPolymer Science and Technology, Vol. 7, pp 431-445, IntersciencePublishers, Division of John Wiley & Sons, New York, N.Y. (1967), thedisclosure of which is expressly incorporated herein by reference.

The acid catalyst used in initiating the furfuryl alcohol resinpolymerization (condensation) is a strong acid, preferably an acidhaving a pK_(a) less than about 3, preferably less than about 2, andmost preferably about 1.5 or less. The acid should be reasonably solublein the components of the curable composition to facilitate distributionthroughout the polymerizable mixture. While it is not essential, it ispreferable that the acid be an organic acid. While the extremely lowpK_(a) acids perform exceptionally well, it is not essential to employextremely strong acids and frequently it is desirable to avoid usingsuch compounds in view of the hazards and corrosive problems createdthereby. Mixtures of acids may be used advantageously. Typical exampleswhich fall within the broad and preferred ranges discussed above aresulfonic acids such as, for example, toluene sulfonic acid, nitrotoluenesulfonic acid, and propane sulfonic acid; dichloro- and trichloroaceticacids, phosphonic acids such as, for example, benzene phosphonic acid.Other useful acids include maleic acid, malonic acid, and acetyleneacids such as, for example, acetylene carboxylic and acetylenedicarboxylic acids. The proportion of acid catalyst contained in thecurable mixture is an effective proportion for catalyzing the furfurylalcohol resin formation and typically this ranges from between about0.01% and about 5% by weight of the furfuryl alcohol resin portion ofthe curable mixture. Of course the acid catalyst is separated from thefurfuryl alcohol resin ingredients prior to polymerization, so thatconventional two-pack technology is practiced.

It should be noted that an additional method for activating the furfurylalcohol resin polymerization reaction involves the generation of aferrocinium ion. A ferrocinium ion can be generated by the reaction offerrocine and a peroxide, the reaction of ferrocine andtrichloromethylsulfonyl chloride, and a variety of additional knownmethods. Heretofore, it was reported that ferrocinium ions were usefulin promoting free radical cure. McGinniss and Stevenson, PolymerPreprints, Vol. 15, pp 302-305 (1974). The use of ferrocinium ions inpromoting acid catalyst-curable reactions was a discovery made duringthe course of developing the present invention. Accordingly, this aspectof the present invention, then, can provide a curable mixture offurfuryl alcohol resin-forming ingredients, acid catalyst, peroxideinitiator, acrylic or other ethylenically unsaturated curable compounds,and ferrocine. A truly unique curable mixture results therefrom.

Another unexpected discovery made during the course of developing thepresent invention and relating to the use of ferrocene involves thediscovery of a new complex catalyst which cures epoxides and othercompounds wherein a ring-opening reaction is involved. This complexcatalyst is a complex of a metallocene, eg. ferrocene, and a diazoniumsalt of a Lewis acid. Aryl diazonium salts are known in the literatureand are easily prepared in high yields by the diazotization of primaryaromatic amines with nitrous acid and the Lewis acid of choice. SuitableLewis acids for this purpose include BF₃, PF₅, AsF₅, SbF₅, FeCl₃, andSbCl₅. Metallocenes include, for example, ferrocene, chromosene,cobaltocene, nickelocene, and manganocene. Ferrocene is the preferredmetallocene. The aryl diazonium moeity of the Lewis acid salt can beprepared from virtually any aromatic primary amine and includes, forexample, 2,5-diethoxy-4-(para-tolylmercapto)benzene,2,4-dichlorobenzene, p-nitrobenzene, p-chlorobenzene,p-(N-morpholino)benzene, 2,5-dichlorobenzene, o-nitrobenzene,2,4,6-trichlorobenzene, 2,4,6-tribromobenzene,4-dimethylaminonapthalene, and like diazonium compounds. The simplemixing of the aryl diazonium salt of a Lewis acid with the metalloceneis sufficient to initiate the ring opening reaction of an epoxidemonomer, oligomer, or polymer. Besides a wide variety of epoxides, otherheterocyclic ring-opening reactions which can be catalyzed with thenovel metallocene-aryl diazonium salt of a Lewis acid catalyst include

cyclic ethers, eg. ##STR11## cyclic formals and acetals, eg. ##STR12##lactones, eg. ##STR13## sulfur-containing ring monomers, eg. ##STR14##organosilicone monomers, eg. ##STR15## The foregoing ring-compounds aresubject to cationic polymerization in the presence of the metallocenearyl diazonium salt of a Lewis acid catalyst as described herein.

The compounds curable by a peroxide initiator often have been referredto as acrylic compounds for convenience and not by way of limitation.Broadly, any ethylenically unsaturated monomer, oligomer, or polymerwhich can be cured or polymerized in the presence of a peroxideinitiator is a suitable compound for use with the novel activatorsystems of the present invention. In adhesives technology, acrylic oracrylate compounds find wide acceptance in the industry. Anothersuitable class of ethylenically unsaturated compounds are vinylcompounds while a third broad class are compounds containing backboneethylenic unsaturation as typified by ethylenically unsaturatedpolyester polymers. Referring with more particularity to reactiveacrylic or acrylate monomers, oligomers, or polymers, a variety of mono-and polyacrylate monomers find use in accordance with the presentinvention. Monoacrylates include allyl acrylate, amyl acrylate, laurylacrylate, isopropyl acrylate, and the like; monomethacrylates include,for example, benzyl methacrylate, stearyl methacrylate, decylmethacrylate, cyclohexyl methacrylate, and the like and mixturesthereof; di- and polymethacrylates include, for example, 1,4-butanedioldimethacrylate, diethylene glycol dimethacrylate, propylene glycoldimethacrylate, and the like and mixtures thereof; and di- andpolyacrylates include, for example, 1,3-butanediol diacrylate,diethylene glycol diacrylate, ethylene glycol diacrylate, polyethyleneglycol diacrylate, tetraethylene glycol diacrylate, and mixturesthereof. The foregoing monomers are merely representative and notlimitative of the list of acrylate and methacrylate monomers suitablefor use in the present invention as those skilled in the art willappreciate. Other suitable reactive compounds for use in the presentinvention include acrylated epoxy resins, acrylated silicone resins,acrylated polysulfide/polysulfone resins, acrylated polyurethane resins,acrylated melamine resins, acrylated urea-formaldehyde resins, and thelike and mixtures thereof. Such acrylate-functional polymers are wellknown in the art and little more about them need be said here.

As noted above, the trend to structural adhesive formulations has beenfacilitated by the development of a new generation of adhesives,so-called second generation acrylic adhesives. Such second generationadhesives are toughened plastics which have been toughened by a varietyof mechanisms. Rubbery particles is an example of a method forincreasing the toughness of a structural adhesive. Further informationon the new generation of acrylic adhesives which can be activatedaccording to the precepts of the present invention can be found in thefollowing selected references: Bennet and Gould, Assembly Engineering,Dec. 1978; Lee, Engineering, p. 1, Nov. 1977; Lyn, Society of AutomotiveEng., Inc., ISSN01487191/79/0228-151 ADHESIVES AGE, p. 34, Oct. 1979,and p. 25, Dec. 1979; Wilkinson, ADHESIVES AGE, p. 20, July 1978; Cookeret al., ADHESIVES AGE, p. 29, Aug. 1977; and U.S. Pat. No. 3,890,407,the disclosures of which are expressly incorporated herein by reference.It will be appreciated that a variety of conventional as well as newacrylic adhesive formulations may be cured in accordance with theprecepts of the present invention.

Vinyl monomers, oligomers, and polymers are another important class ofethylenically unsaturated compounds which can be cured with a peroxideinitiator. Suitable such vinyl compounds include, for example, vinylesters of aliphatic and aromatic carboxylic acids, polybutadiene-basedcompounds, and like vinyl compounds.

A third important class of ethylenically unsaturated compounds areethylenically unsaturated polyester resins generally containing fumerateor maleate unsaturation and prepared from aromatic or aliphatic dibasicacids or dianhydrides and difunctional alcohols as more particularlypointed out in "Preparative Methods of Polymer Chemistry", W. R.Sorenson and T. W. Campbell, pp 445-452, Interscience Publishers,Division of John Wiley & Son, New York, N.Y., (1968), the disclosure ofwhich is expressly incorporated herein by reference. The ethylenicunsaturation additionally may be contained in a monomer chain or in aside chain pendantly attached to the polymer. In making an ethylenicallyunsaturated polyester, for example, the hydroxyl component can be apolyol or monomeric alcohol provided from a polyester, polyether,polyurethane, polysulfide, polyamide, and the like. The ethylenicunsaturation can be provided by the monomeric alcohol or polyol itselfor can be reacted onto a polyol or monomeric alcohol subsequently byconventional reaction schemes. Examples of such schemes include reactingthe monomeric alcohol or polyol with, for example, acrylic acids,acrylyl halides, acrylic-terminated ethers, acrylic or methacrylicanhydrides, isocyanate-terminated acrylates, epoxy acrylates, and thelike. Further reaction schemes for formulating such polymers includereacting hydroxy-acrylate monomer, hydroxy methacrylate monomer, or anallyl ether alcohol with a cyclic anhydride such as, for example, theanhydrides: maleic, phthalic, succinic, norborine, gluteric, and thelike. The product unsaturated polyester additionally then can be reactedwith a suitable oxirane compound, such as, for example, ethylene oxide,propylene oxide, glycidyl acrylate, allyl glycidyl ether, alpha-olefinepoxide, butyl glycidyl ether, and the like. Suitable allyl alcoholsinclude, for example, trimethylol propane monoallyl ether, trimethylolpropane diallyl ether, allyl-hydroxy propyl ether, and the like.Additionally, conventional reaction schemes include reactingalpha-aliphatic or aromatic substituted acrylic acids with an oxiranecompound, and reacting the hydroxy acrylate or hydroxy methacrylate witha di-mercaptan compound. Any of the foregoing reaction schemes as wellas other conventional reaction schemes can be used as is necessary,desirable, or convenient in conventional fashion. As can be seen fromthe discussions above, ethylenic unsaturation functionality can beattached to a variety of polymers including polyesters, polyurethanes,silicones, epoxides, polyethers, polysulfides, polysulfones, polyamides,and the like.

In addition to the curable portion of the mixture, non-reactivethermoplastic polymeric species may be included for a variety of specialeffects. In the adhesive art, such non-reactive thermoplastic polymersinclude rubbers such as chlorinated rubbers and chlorinatedpolyethylenes, thermoplastic acrylic polymers, polyester polymers,polyurethanes, silicone polymers, epoxide resins, polyether resins,polysulfide resins, polysulfone resins, polyamide resins, and the like.Additionally, the curable mixture may contain organic cosolvent, thoughoften such cosolvent is unnecessary especially in adhesive applications.A variety of conventional inert fillers also may be contained in thecurable mixture as can conventional opacifying and tinctorial pigments.For preferred structral adhesive applications, though, fillers andpigments generally are unnecessary.

A variety of conventional peroxide initiators can be activated accordingto the precepts of the present invention. Representative of suchperoxides include, for example, tert-butyl peroxide, hydrogen peroxide,benzoyl peroxide, cumene hydroperoxide, tetraline hydroperoxide,diisopropyl benzene hydroperoxide, acetyl peroxide, urea peroxide,methyl ethyl ketone peroxide, diisopropyl ether peroxide, and the like,and mixtures thereof. Organic hydroperoxides and peresters may be used,though simple peroxides are preferred. Preferably, the peroxideinitiator comprises from about 0.1 to about 5% by weight of thecomposition.

The curable mixture of the present invention is provided in two or morepackages as the presence of the activator with the peroxide curing agentwill provide a rapid set or cure of the curable mixture. So long as theperoxide initiator and the activator are contained in separate packages,the various resins or curable portion of the mixture may be contained ineither package as is necessary, desirable, or convenient in conventionalfashion. The two packages are mixed just prior to application and,depending upon the formulation, working time can be as short as a fewseconds on up to several minutes. Conventional structural adhesiveapplication techniques then are employed.

The following examples show how the present invention can be practicedbut should not be construed as limiting. In this application, allpercentages and proportions are by weight, all units are in the metricsystem, and all citations are expressly incorporated herein byreference.

IN THE EXAMPLES EXAMPLE 1

A Cu⁺¹ catalyst system was prepared by adding 2.5 g of cuprous chlorideto 2 g of water followed by the further addition of 2 g of ascorbicacid. The green colored impure aqueous cuprous chloride solution turnedwhite indicating that it was ready for use.

Several acrylic resins were formulated, admixed with 2% by weight of theCu⁺¹ catalyst system described above, and 3%-5% by weight of cumenehydroperoxide, and the set times thereof recorded. The set time is thetime required for the liquid mixture to gel to a solid intractable mass.The following acrylic resins were evaluated with the following results.

                  TABLE 1                                                         ______________________________________                                                                         Set                                          Run                              Time                                         No.  Acrylic Resin               (min.)                                       ______________________________________                                        1    Trimethylolpropane triacrylate                                                                            1                                            2    reaction product of acrylic acid (2 moles)                                                                1                                                 and the diglycidyl ether of bis-phenol                                        A (1 mole) (Epoxy-Acrylate)                                              3    PURELAST 166 urethane acrylate                                                                            1                                                 (Polymer Systems Corporation)                                            4    equal weight blend of acrylated polyester                                                                 12                                                (1 mole triethylene glycol, 1 mole                                            ethylene glycol, 1 mole 1,3-butylene                                          glycol, 1 mole isophthalic acid,                                              1 mole adipic acid-terminated with                                            acrylic acid) and hydroxyethylacrylate                                        (see Paint and Varnish Production, Vol. 64,                                   No. 8, 32-36, August 1974)                                               5    same as Run No. 4 plus 10%  30                                                of a silicone modified thermoplastic                                          polyester as described in Paint and                                           Varnish Production, pages 35-43 (January 1972)                           ______________________________________                                    

When Run No. 3 was repeated using only 2.5% ascorbic acid and 2.5%cumene hydroperoxide (control), the urethane acrylate resin did not setafter 24 hours. The efficacy of using the Cu⁺¹ catalyst system, thus, isdemonstrated.

EXAMPLE 2

In this example, the Cu⁺¹ catalyst was complexed with a monomer orpolymer which acted as a substrate or carrier for the catalyst. The Cu⁺¹complex (0.05-5% by weight) was added to various of the acrylic resinsdescribed in Example 1 and the set times of the resulting mixturesrecorded. The Cu⁺¹ complex was synthesized from 30 g of the complexingmonomer or polymer and 3 g of Cu⁺¹ powder. The following results wereobtained.

                  TABLE 2                                                         ______________________________________                                                                             Set                                      Run  Complexing Monomer              Time                                     No.  or Polymer        Acrylic Resin*                                                                              (min.)                                   ______________________________________                                        1    Methanol          Urethane acrylate                                                                            1                                                              (PURELAST 166)                                         2    Propylene glycol  Urethane acrylate                                                                            1                                                              (PURELAST 166)                                         3    Hydroxyethyl methacrylate                                                                       Epoxy-Acrylate                                                                               2                                       4    Allyl alcohol     Acrylated Polyester                                                                         10                                       5    Allyl acetate     Acrylated Polyester                                                                         10                                       6    Polybutadiene     Urethane acrylate                                                                           10                                            (liquid, Nisseki B-1500                                                                         (PURELAST 166)                                              polybutadiene)                                                           7    Allyl methacrylate                                                                              Urethane acrylate                                                                           10                                                              (PURELAST 166)                                         8    Acrylic acid adduct of                                                                          Urethane acrylate                                                                           10                                            dicyclopentadiene acrylate                                                                      (PURELAST 166)                                         9    Modified polybutadiene resin                                                                    Epoxy-Acrylate                                                                              10                                            (HYCAR reactive liquid                                                        polymer VTBN 1300 × 22,                                                 B. F. Goodrich)                                                          ______________________________________                                         *Refer to Table 1 for complete details.                                  

Again, the above-tabulated results demonstrate that the Cu⁺¹ can becomplexed and such complex function as an effective activator for theperoxide initiator. Such complex results in greater catalyst (Cu⁺¹)efficiency and provides a homogenous solution or dispersion of theactivator complex in the curable mixture.

EXAMPLE 3

In order to demonstrate the dramatic and unexpected improvement inacrylic formulations cured with the Cu⁺¹ catalyst system, three priorart catalyst systems were compared to the inventive Cu⁺¹ catalystsystem. The acrylic formulation is described in U.S. Pat. No. 4,230,834and consisted of the following acrylic monomers: methyl methacrylate(1681 parts), methacrylic acid (204 parts), epoxy acrylate of Example 1(100 parts), 1,3-butylene dimethacrylate (136 parts); a thermoplasticadditive being chlorosulfonated polyethylene (1224 parts); and cumenehydroperoxide (34 parts). The catalyst systems evaluated and the resultsobtained are displayed in the following table.

                  TABLE 3                                                         ______________________________________                                                                    Set     Tensile.sup.(b)                           Run                         Time    Strength                                  No.  Catalyst System.sup.(a)                                                                              (min.)  (kg/cm.sup.2)                             ______________________________________                                        1    1% ferrocene           4       35.15                                          1% toluene sulfonic acid                                                      2% cumene hydroperoxide                                                  2    2% N,N--dimethyl aniline                                                                             60      14.06                                          2% cumene hydroperoxide                                                  3    1% butyraldehyde-butyl amine product                                                                 4       49.21                                          0.025% copper (+2) napthanate                                            4    1% Cu.sup.+1           4       98.42                                          1% ascorbic acid                                                         ______________________________________                                         .sup.(a) Run 1: U.S. Pat. No. 3,855,040                                        Run 3: U.S. Pat. No. 4,230,834                                               .sup.(b) ASTM test D1002                                                 

The above-tabulated results demonstrate the unexpectedly excellenttensile strength which the Cu⁺¹ catalyst system provides in curingacrylic formulations.

EXAMPLE 4

In order to demonstrate the furfuryl alcohol/acid catalyst activator orsystem, comparative curable formulations with and without furfurylalcohol were prepared. The results obtained appear below:

                  TABLE 4                                                         ______________________________________                                                       Cumene   Organic.sup.(2)                                                      Hydro-   Sulfonic                                                                              Furfuryl.sup.(3)                              Run  Acrylate.sup.(1)                                                                        peroxide Acid    Alcohol Set Time                              No.  Resin     (wt %)   (wt %)  (wt %)  (min)                                 ______________________________________                                        1    PES 166   5.0      5.0     --      No cure                               2    PES 166   5.0      5.0     5.0     30                                    3    PES 166   10.0     10.0    10.0    30                                    ______________________________________                                         .sup.(1) PES 166 is PURELAST 166 urethane acrylate of Example 1. All          percentages are by weight of the PES 166 resin.                               .sup.(2) ChemRez C2009 organic sulfonic acid, Ashland Chemical Company,       Columbus, Ohio.                                                               .sup.(3) ChemRez 200 furfuryl alcohol, Ashland Chemical Company.         

The above-tabulated results demonstrate that the furfuryl alcohol curegenerates adequate heat at room temperature to activate the peroxideinitiator for cure of the acrylic resin. Note that only a smallproportion of the furfuryl alcohol was required in order to activatesuch cure.

EXAMPLE 5

This example demonstrates the new catalyst system for heterocyclic ringcompounds. Two packages were prepared. The first package containedpara-nitrobenzene-diazonium fluoroborate (5% by weight of epoxy resinplus 2% water). The second package contained 5% ferrocene in thediglycidyl ether of bis-phenol A (EPON 828 resin, Shell ChemicalCompany). The two packages when mixed resulted in a cured polymericnetwork in 30 minutes at room temperature.

EXAMPLE 6

Three different modified epoxy resin adhesion promoters were prepared inaccordance with the procedure found in Sorenson and Campbell,Preparative Methods of Polymer Chemistry, supra. Two moles of DER 333epoxy resin (diglycidyl ether of bisphenol A, Dow Chemical Company) werereacted with one mole of bis-phenol A in the presence of 0.1-1% ofbenzyldimethyl amine catalyst. Two variations of the modified epoxyresin adhesion promoter then were made by the further reaction with onemole of acrylic acid and two moles of acrylic acid. The three modifiedepoxy resin adhesion promoters can be represented as follows: ##STR16##

EXAMPLE 7

The procedure of Example 6 was repeated, exept that the bisphenol Aepoxy resin was replaced with 4,4'-dihydroxy-diphenylsulfone. ##STR17##

EXAMPLE 8

The procedure of Example 6 was repeated, except that the bisphenol A wasreplaced with 4-4'-dihydroxydiphenylsulfide. ##STR18##

EXAMPLE 9

A two-package acrylic adhesive formulation was prepared from 20% byweight of each of the adhesion promoters of Examples 6-8, 50% by weightmethyl methacrylate, and 30% by weight of PURELAST 166 urethane acrylateof Example 1. The catalyst system comprised Cu⁺¹ (1% by weight) andcumene hydroperoxide (2% by weight). Each of the nine adhesivecompositions were cured at room temperature for 24 hours between two2.54 cm×15.24 cm (1"×16") steel coupons.

Thereafter, sets of the bonded coupons were subjected to stressing byimmersion in boiling water for one hour and by immersion in chloroformsolvent for 5 hours. The lap shear adhesively bonded coupons then weresubjected to evaluation by attempting to pull them apart by hand. Thefollowing results were obtained.

                  TABLE 5                                                         ______________________________________                                                      Boiling Water*                                                                            Chloroform*                                         Promoter No.  Immersion   Immersion                                           ______________________________________                                        6A            No          No                                                  6B            No          Some                                                6C            No          No                                                  7A            Yes         No                                                  7B            Yes         Yes                                                 7C            No          No                                                  8A            Yes         No                                                  8B            Yes         Yes                                                 8C            No          No                                                  ______________________________________                                         *No: easily pulled apart by hand                                              Some: harder to pull apart, but bond does fail                                Yes: very difficult to pull apart or cannot be pulled apart by hand.     

The above-tabulated results show that only the mono-functionalsulfone/sulfide resins, Promoters 7B and 8B, imparted sufficientadhesion so that both the boiling water and the solvent immersion testscould be passed.

EXAMPLE 10

A series of two-package adhesive formulations catalyzed with Cu⁺¹ wasprepared, cured at room temperature between two coupons and their shearstrengths recorded. The formulations and results obtained appear below.

                  TABLE 6                                                         ______________________________________                                                            Formulation No. (g)                                       Ingredient            7-22    7-23   7-24                                     ______________________________________                                        Part A                                                                        Epoxy Acrylate.sup.(1)                                                                              9       9      5                                        Methacrylic Acid      1       1      1                                        PES 166.sup.(2)       --      --     3                                        Acrylic Oligomer.sup.(3)                                                                            --      --     2                                        Bis(methacryloxy ethyl) Phosphate.sup.(4)                                                           0.3     0.3    0.3                                      Cumene hydroperoxide  1       1      0.7                                      Part B                                                                        Acrylic Oligomer.sup.(3)                                                                            00      00     2                                        Epoxy Acrylate.sup.(1)                                                                              9       9      5                                        Cu.sup.+1 Complex A.sup.(5)                                                                         1       --     1                                        Cu.sup.+1 Complex B.sup.(6)                                                                         --      1      --                                       PES 166.sup.(2)       --      --     3                                        Shear Strength (kg/cm.sup.2)                                                                        105.6   81.6   130.0                                    ______________________________________                                         .sup.(1) Grade 40 BH epoxy acrylate, Dai Nippon Ink Chemicals Co., Tokyo,     Japan                                                                         .sup.(2) PURELAST 166 urethane acrylate of Example 1                          .sup.(3) ARONICS M7200 acrylic oligomer, Toa Gosei Co., Tokyo, Japan          .sup.(4) Grade JPA514 bis(methacryloxy ethyl) phosphate, Johhoku Chemical     Co., Tokyo Japan                                                              .sup.(5) CuCl.sub.2  25 parts                                                 Allyl alcohol  2.5 parts                                                       Ascorbic acid  2.5 parts                                                     .sup.(6) Grade JPA514 bis(methacryloxy ethyl) phosphate  25 parts             CuCl.sub.2.2H.sub.2 O  2.5 parts                                         

The above-tabulated results demonstrate the excellent shear strengthproperties of acrylic adhesives cured with the novel Cu⁺¹ catalystcomplex of the present invention.

EXAMPLE 11

Another series of two-package Cu⁺¹ catalyzed adhesive formulations wereprepared and their shear strength evaluated with the following results.

                  TABLE 7                                                         ______________________________________                                                  Formulation No. (g)                                                 Ingredient  8-13   8-14   8-15 8-16 8-17 8-18 8-19                            ______________________________________                                        Part A                                                                        Epoxy Acrylate                                                                            9      9      9    9    9    9    9                               40BH                                                                          Methacrylic Acid                                                                          1      1      1    1    1    1    1                               Bis(methacryloxy                                                                          0.3    0.3    0.3  0.3  0.3  0.3  0.3                             ethyl).sup.(1) phosphate                                                      Cumene Hydro-                                                                             0.7    0.7    0.7  0.7  0.7  0.7  0.7                             peroxide                                                                      Part B                                                                        Epoxy Acrylate                                                                            8.7    8.7    8.7  8.7  8.7  8.7  8.7                             40BH.sup.(1)                                                                  Methacrylic Acid                                                                          1      1      1    1    1    1    1                               Bis(methacryloxy                                                                          0.3    0.3    0.3  0.3  0.3  0.3  0.3                             ethyl).sup.(1) phosphate                                                      Cu.sup.+1 Complex                                                                         0.5    0.3    0.2  0.1  0.05 --   --                              DEG.sup.(2)                                                                   Cu.sup.+1 Complex                                                                         --     --     --   --   --   0.3  --                              1.2P.sup.(3)                                                                  Cu.sup.+1 Complex                                                                         --     --     --   --   --   --   0.3                             1.3P.sup.(4)                                                                  Set Time (min)                                                                            3-4    2      3    5-6  5-6   2   1                               Shear Strength                                                                            49.8   73.0   72.2 74.1 90.6 73.6 47.7                            (kg/cm.sup.2).sup.(5)                                                         ______________________________________                                         .sup.(1) See Table 6, Example 10                                              .sup.(2) Diethylene glycol  30 g                                              CuCl.sub.2.2H.sub.2 O  3 g                                                    Ascorbic Acid  3 g                                                            .sup.(3) 1,2propane diol  30 g                                                CuCl.sub.2.2H.sub.2 O  3 g                                                    Ascorbic Acid  3 g                                                            .sup.(4) 1,3propane diol  30 g                                                CuCl.sub.2.2H.sub.2 O  3 g                                                    Ascorbic Acid  3 g                                                            .sup.(5) Room temperature cure for 72 hours; average of 3 samples;            cohesive failure only for sample no. 816, 817, and 818.                  

The above-tabulated results again demonstrate the rapid set times andexcellent hard strengths that are achieved with the novel Cu⁺¹ complexcatalyst.

EXAMPLE 12

Several more two-package Cu⁺¹ catalyzed adhesive formulations wereprepared and evaluated as follows.

                                      TABLE 8                                     __________________________________________________________________________                   Sample No. (g)                                                 Ingredient     8-41                                                                             8-42                                                                             8-43                                                                             8-44                                                                             8-45                                                                             8-46                                                                             8-47                                                                             8-48                                                                             8-49                                                                             8-50                                __________________________________________________________________________    Part A                                                                        Epoxy Acrylate 40BH.sup.(1)                                                                  6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                 Methacrylic Acid                                                                             1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                 Bis (methacryloxy ethyl).sup.(1)                                                             0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                 phosphate                                                                     Cumene Hydroperoxide                                                                         0.7                                                                              0.7                                                                              0.7                                                                              0.7                                                                              0.7                                                                              0.7                                                                              0.7                                                                              0.7                                                                              0.7                                                                              0.7                                 Hexanediol diacryalate                                                                       1.5                                                                              -- -- -- -- -- -- -- -- --                                  Acrylic oligomer 3GT.sup.(2)                                                                 -- 1.5                                                                              -- -- -- -- -- -- -- --                                  Triallyl isocyanurate                                                                        -- -- 1.5                                                                              -- -- -- -- -- -- --                                  Trimethylolpropane                                                                           -- -- -- 1.5                                                                              -- -- -- -- -- --                                  Epoxy (polyoxyethylene).sup.(3)                                                              -- -- -- -- 1.5                                                                              -- -- -- -- --                                  acrylate-4                                                                    Epoxy (polyoxyethylene).sup.(4)                                                              -- -- -- -- -- 1.5                                                                              -- -- -- --                                  acrylate-2.6                                                                  Hydroxypropyl Methacrylate                                                                   -- -- -- -- -- -- 1.5                                                                              -- -- --                                  2-Hydroxy ethyl methacrylate                                                                 -- -- -- -- -- -- -- 1.5                                                                              -- --                                  Triacrylate PE-3A.sup.(5)                                                                    -- -- -- -- -- -- -- -- 1.5                                                                              --                                  Hemi Caprolactone.sup.(6)                                                                    -- -- -- -- -- -- -- -- -- 1.5                                 Part B                                                                        Epoxy Acrylate 40BH.sup.(1)                                                                  6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                                                              6.5                                 Methacrylic Acid                                                                             1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                                                              1.0                                 Bis (methacryloxy ethyl).sup.(1)                                                             0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                                                              0.3                                 phosphate                                                                     Hexanediol diacryalate                                                                       1.5                                                                              -- -- -- -- -- -- -- -- --                                  Acrylic oligomer 3GT.sup.(2)                                                                 -- 1.5                                                                              -- -- -- -- -- -- -- --                                  Triallyl isocyanurate                                                                        -- -- 1.5                                                                              -- -- -- -- -- -- --                                  Trimethylolpropane                                                                           -- -- -- 1.5                                                                              -- -- -- -- -- --                                  Epoxy (polyoxyethylene).sup.(3)                                                              -- -- -- -- 1.5                                                                              -- -- -- -- --                                  acrylate-4                                                                    Epoxy (polyoxyethylene).sup.(4)                                                              -- -- -- -- -- 1.5                                                                              -- -- -- --                                  acrylate-2.6                                                                  Hydroxypropyl Methacrylate                                                                   -- -- -- -- -- -- 1.5                                                                              -- -- --                                  2-Hydroxy ethyl methacrylate                                                                 -- -- -- -- -- -- -- 1.5                                                                              -- --                                  Triacrylate PE-3A.sup.(5)                                                                    -- -- -- -- -- -- -- -- 1.5                                                                              --                                  Hemi Caprolactone.sup.(6)                                                                    -- -- -- -- -- -- -- -- -- 1.5                                 Cu.sup.+1 Complex 1.2P.sup.(7)                                                               0.1                                                                              0.1                                                                              0.1                                                                              0.1                                                                              0.1                                                                              0.1                                                                              0.1                                                                              0.1                                                                              0.1                                                                              0.1                                 Set Time (min) 25 15 8  8  10 9  17 13 60 60                                  Shear strength (kg/cm.sup.2).sup.(8)                                                         74.4                                                                             66.9                                                                             77.3                                                                             55.4                                                                             83.2                                                                             82.1                                                                             76.2                                                                             97.0                                                                             85.3                                                                             91.2                                __________________________________________________________________________     .sup.(1) See Table 6, Example 10                                              .sup.(2) Acrylic Oligomer 3GT, Shinnakamura Chemical Co., Wakayama, Japan     .sup.(3) Grade BPE4 epoxy(polyoxyethylene) acrylate, Shinnakamura Chemica     Co., Wakayama, Japan                                                          .sup.(4) Grade BPE2.6 epoxy(polyoxyethylene) acrylate, Shinnakamura           Chemical Co., Wakayama, Japan                                                 .sup.(5) Grade PE3A triacrylate, Shinnakamura Chemical Co., Wakayama,         Japan                                                                         .sup.(6) PLACCEL FM1 hemi caprolactone, Diacel Co., Osaka, Japan              .sup.(7) See Table 7, Example 11                                              .sup.(8) Room temperature cure for 63 hours; average of 3 samples.       

Again, the invention is demonstrated with respect to the Cu⁺¹ complexfor use with a two-pack acrylic adhesive.

EXAMPLE 13

Additional two-package Cu⁺¹ catalyzed adhesive formulations wereprepared and evaluated as follows.

                                      TABLE 9                                     __________________________________________________________________________                   Sample No. (g)                                                 Ingredient     10-44                                                                             10-45                                                                             10-46                                                                             10-47                                                                             10-48                                                                             10-49                                                                             10-50                                                                             10-51                                                                            10-52                           __________________________________________________________________________    Part A                                                                        Cumene hydroperoxide                                                                         3   3   3   3   3   3   3   3  3                               Bis (methacryloxy ethyl).sup.(1)                                                             3   3   3   3   3   3   3   3  3                               phosphate                                                                     Methacrylic Acid                                                                             9   9   9   9   9   9   9   9  9                               2-Hydroxy ethyl                                                                              10  10  10  10  10  10  10  10 10                              methacrylate                                                                  Triallyl isocyanurate                                                                        5   5   5   5   5   5   5   5  5                               Epoxy acrylate oligomer.sup.(2)                                                              55  45  35  20  10  60  50  -- --                              EPN-1000 XC                                                                   Urethane Acrylic Oligomer.sup.(3)                                                            10  20  30  45  55  --  --  60 50                              HO-MPP-U                                                                      Epoxy Acrylate Oligomer.sup.(4)                                                              5   5   5   5   5   10  25  10 20                              VR-90                                                                         Bis (methacryloxy ethyl).sup.(1)                                                             3   3   3   3   3   3   3   3  3                               phosphate                                                                     Methacrylic Acid                                                                             10  10  10  10  10  10  10  10 10                              2-Hydroxy ethyl                                                                              10  10  10  10  10  10  10  10 10                              methacrylate                                                                  Triallyl isocyanurate                                                                        5   5   5   5   5   5   5   5  5                               Epoxy acrylate oligomer.sup.(2)                                                              55  45  35  20  10  60  50  -- --                              EPN-1000 XC                                                                   Urethane Acrylic Oligomer.sup.(3)                                                            10  20  30  45  55  --  --  60 50                              HO-MPP-U                                                                      Epoxy Acrylate Oligomer.sup.(4)                                                              5   5   5   5   5   10  25  10 20                              VR-90                                                                         Cu.sup.+1 Complex DEG.sup.(5)                                                                2   5   5   5   5   5   5   5  5                               Set Time (min) 140 90  70  60  20  120 120 6  3                               Shear Strength (kg/cm.sup.2).sup.(6)                                                         90.8                                                                              113.3                                                                             158.3                                                                             158.3                                                                             131.7                                                                             143.3                                                                             111.7                                                                             76.7                                                                             96.7                            __________________________________________________________________________     .sup.(1) See Table 6, Example 10                                              .sup.(2) Grade EPN1000XC epoxy acrylate oligomer, Showa Kobunshi Co.,         Tokyo, Japan                                                                  .sup.(3) Grade HOMPP-U urethane acrylate oligomer, Hyoeisha Yshi Co.,         Osaka, Japan                                                                  .sup.(4) Grade VR90 epoxy acrylate oligomer, Showa Kobunshi Co., Tokyo,       Japan                                                                         .sup.(5) See Table 7, Example 11                                              .sup.(6) Room temperature cure for 24 hours; average of 2 runs.          

The performance of the Cu⁺¹ complex is yet again confirmed.

I claim:
 1. A catalyst system capable of effecting room temperature cureof a curable mixture comprising at least one ethylenically-unsaturatedcompound which comprises a Cu⁺¹ activator and a peroxide initiator. 2.The catalyst system of claim 1 which additionally comprises a reducingagent.
 3. The catalyst system of claim 2 wherein said reducing agent isselected from the group consisting of ascobic acid, sodium sulfite,sodium bisulfite, sodium metabisulfate, and mixtures thereof.
 4. Thecatalyst system of claim 3 wherein said reducing agent is ascorbic acid.5. The catalyst system of claim 1 wherein said Cu⁺¹ activator is a Cu⁺¹olefin complex or a Cu⁺¹ hydroxyl complex.
 6. The catalyst system ofclaim 5 wherein said olefin of said complex is a vinyl or acrylicmonomer, oligomer, or polymer.
 7. The catalyst system of claim 5 whereinsaid olefin or said hydroxyl compound of said complex is selected fromone of the following: ##STR19## where R₁ is --H, ##STR20## where R₂ is##STR21## R₃ is --H or --CH₃, ##STR22## where R₄ is H or a lower alkylgroup, X is --O--, ##STR23## where Z is --CH₂ --CH₂ --O--_(n).
 8. Thecatalyst system of claim 1 wherein said peroxide initiator is selectedfrom the group consisting of tert-butyl peroxide, hydrogen peroxide,benzoyl peroxide, cumene hydroperoxide, tetraline hydroperoxide,diisopropyl benzene hydroperoxide, acetyl peroxide, urea peroxide,methyl ethyl ketone peroxide, diisopropyl ether peroxide, and mixturesthereof.